Method for production of methyl isobutyl ketone

ABSTRACT

A novel method for producing methyl isobutyl ketone from acetone and hydrogen in one stage with improved conversion and selectivity by contacting acetone in liquid phase with hydrogen in the presence of a catalyst of (a) palladium and synthetic zeolite, or (b) palladium and alumina together with or without thorium oxide, zirconium oxide and/or chromium oxide, at a temperature of 100* to 250* C. and under a partial pressure of hydrogen of 0.1 to 10 kg per square centimeter.

United States Patent Takagiet al.

[ 51 May 30, 1972 [54] METHOD FOR PRODUCTION OF METHYL ISOBUTYL KETONE[72] Inventors: Kazumi Takagi; Masahiro Murakami;

Koichi Iketani, all of Niihama-shi, Japan [73] Assignee: Sumitomo.Chemical Company, Ltd.,

Osaka, Japan [22] Filed: Oct. 6, 1969 [21] App]. No.: 864,173

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 1,015,003 12/1965Great Britain ..260/593 R 4,024,977 1/1965 Japan ..260/593 R 592,1012/1960 Canada ..260/593 R Primary E.xaminerDaniel D. HorwitzAtt0rneyStevens, Davis, Miller & Mosher ABSTRACT A novel method forproducing methyl isobutyl ketone from acetone and hydrogen in one stagewith improved conversion and selectivity by contacting acetone in liquidphase with hydrogen in the presence of a catalyst of (a) palladium andsynthetic zeolite, or (b) palladium and alumina together with or withoutthorium oxide, zirconium oxide and/or chromium oxide, at a temperatureof 100 to 250 C. and under a partial pressure of hydrogen of 0.1 to 10kg per square centimeter.

2 Claims, No Drawings METHOD FOR PRODUCTION OF METHYL ISOBUTYL KETONEThe present invention relates to a method for producing methyl isobutylketone in one-stage from acetone and hydrogen in liquid phase.

Methyl isobutyl ketone (referred to MIBK hereinafter), which is usefulas an organic solvent and an ingredient of paints and the like, has beenconventionally synthesized from acetone and hydrogen according to thefollowing reaction scheme:

2UU3 (|J CH3 condensation acetone 2 S dehydration H O H diacetonealcohol (D AA) C=OH- C-CH H O I H C mesityl oxide hydrogenationCH-CHz-C-CH: (M

HgC H C\ meth lisobut lket n /CCH:-(|JCH3 y y o e MIBK HQC isomesityloxide (IMO) In the most common practice, the steps of condensation,dehydration and hydrogenation have been, hitherto, conductedsuccessively in the order given above. Thus, the conventional processcomprises contacting in liquid phase under atmospheric pressure acetonewith a solid alkaline catalyst such as barium hydroxide and the like ata temperature of to 20 C. to produce diacetone alcohol with a conversionof about percent owing to an equilibrium of the reaction, separating theresulting diacetone alcohol from unreacted acetone, subjecting thealcohol to dehydration by heating at a temperature of 100 to 120 C. inliquid phase in the presence of an acid catalyst such as sulfuric acid,phosphoric acid and the like to form mesityl oxide and isomesityl oxide,separating and purifying the resulting mixture of oxides, and thensubjecting the mixture of oxides to hydrogenation in vapor phase at atemperature of 140 to 150 C. under atmospheric pressure over a catalystof copper-type or of palladium-type supported on alumina, silica orcarbon and the like to form MIBK. The over-all selectivity for MIBK isabout 80 to 85 percent.

Another process is known to produce MlBK directly from acetone bysubjecting the latter in liquid phase to the reaction with hydrogenunder a pressure of atmospheres at a temperature of 100 to 150 C. in thepresence of an ion-exchange resin of acid-type, which catalyzescondensation and dehydration, and of palladium-carbon, which catalyzeshydrogenation (German Pat. No. 1238453).

However, in the conventional process, three steps of operation, i.e.,condensation, dehydration and hydrogenation, are necessary, and,moreover, the separation and purification of the intermediate productssuch as diacetone alcohol and mesityl oxides are necessary betweensteps, resulting in complication of the operation and lowering of theover-ll yield.

In the process for manufacturing MIBK directly from acetone by the aidof acid-type ion-exchange resin and palladium-carbon as catalysts, therestill exist two significant disadvantages, despite the improvementsattained in the simplified operation and comparatively high selectivity.A disadvantage is a low conversion of acetone, which means a low yieldof MIBK per unit volume of catalyst, owing to the low rate of reactionresulted from the low reaction temperature, since the upper limit set bythe nature of the ion-exchange resin is at about 150 C. Otherdisadvantage is the use of a mixture of two catalysts of the entirelydifferent properties, i.e., acid-type ion-exchange resin andpalladium-carbon; said mixture is difficult to be distributedhomogeneously in the reactant charge, and is inconvenient to handle; andthe large volume occupied by the mixture tends to make the reactoruneconomical.

-An object of the present invention is to provide a method for producingMIBK, without foregoing disadvantages of the prior art, by simpleoperation and with excellent conversion and selectivity.

The present invention provides a method for producing MlBK directly fromacetone in one-stage operation, which comprises contacting acetone withhydrogen in liquid phase in the presence of a catalyst of (a) palladiumand synthetic zeolite (Catalyst A), or (b) palladium and aluminatogether with or without thorium oxide, zirconium oxide and/or chromiumoxide (Catalyst B), at a reaction temperature of to 250 C. under apartial pressure of hydrogen in the reaction system within the range of0.1 to 10 kg. per square centimeter.

The present invention will be more particularly explained by thefollowing description.

Catalyst A may be prepared by impregnating synthetic zeolite with anaqueous solution of palladium salt, and reducing the salt supported onthe synthetic zeolite to palladium metal. Examples of the palladium saltinclude palladium chloride and nitrate. The reducing may be effected,for example, with an aqueous solution of hydrazine or with hydrogen ingaseous phase. Alternatively, active carbon, alumina, silica or the likeis impregnated with an aqueous solution of palladium salt, and afterbeing reduced to the palladium metal in the same way as mentioned above,it may be admixed with synthetic zeolite. The amount of palladium metalsupported on the synthetic zeolite is 0.2 to 3.0 percent by weight. Whenused in admixture with synthetic zeolite, the ratio of synthetic zeoliteto the palladium-loaded carrier may be varied optionally within therange of 1 0.1 to l 10 by weight.

Catalyst B may be preferably prepared by impregnating alumina with anaqueous solution of palladium salt and reducing the salt supported onthe alumina to palladium metal as usual with an aqueous solution ofhydrazine or with hydrogen in gaseous phase. Catalyst B containingthorium oxide, zirconium oxide and/or chromium oxide is preferablyprepared by impregnating alumina with an aqueous solution of the mixtureof thorium, zirconium and/or chromium salt (such as nitrate andchloride) and palladium salt, drying and heating the impregnated aluminain the air to convert the salt supported on alumina into oxide, andsubsequently reducing palladium salt to palladium metal as usual with anaqueous solution of hydrazine or with hydrogen in gaseous phase. Anyactivated alumina may be used as the component material, butgammaalumina is preferable. in the present process alumina componentwould have a catalytic action mainly for the condensation anddehydration reactions. The amount of palladium supported on alumina ispreferably 0.1 to 5.0 percent by weight, and in case that thorium oxide,zirconium oxide and/or chromium oxide is also supported on alumina, theamount of the oxide in the catalyst is preferably 2 to 30 percent byweight. Palladium metal and said oxide would have a catalytic actionmainly for the hydrogenation reaction.

The reaction of the present invention is carried out in liquid phaseunder hydrogen pressure. Reaction temperatures from 100 to 250 C.,preferably from to 210 C. should be used, since at lower temperaturesthe amount of diacetone alcohol, which is an intermediate product of thereaction, tends to increase in the final product, whereas at highertemperatures the amount of by-products such as diisobutyl ketone,mesitylene and the like tends to increase. Preferable reaction time is0.5 to 5 hours.

During the course of reaction, while acetone presents its own vaporpressure corresponding to the reaction temperature, hydrogen should beintroduced into the reacting system so as to maintain its partialpressure at 0.1 to 10 kg. per square centimeter, preferably at 0.5 to 5kg. per square centimeter. The amount of catalyst to be used ispreferably to 100 wt. percent based on acetone used.

The reaction may be carried out either continuously or batch-wise. Inthe continuous operation hydrogen is preferably supplied so as tomaintain constant partial pressure while feeding acetone in constantflow. 1n the batch-wise operation, as soon as the partial pressure ofhydrogen in the reacting system decreases as the reaction proceedshydrogen should be supplied to maintain its partial pressure at thedesired level. After the reaction, the reaction product is distilled toseparate MIBK, unreacted acetone and minor quantities of lay-products,and the unreacted acetone is recycled to the reaction.

Example of the selectivity at the acetone conversion of 30 to 60 percentis 93 to 98 percent for MIBK, O to 1.5 percent for mesitylene, 0 to 0.3percent for mesityl oxide (including isomesityl oxide), 0.1 to 1.5percent for isopropyl alcohol, 0.5 to 4.2 percent for diisobutyl ketone,0 to 2.5 percent for 4,6- dimethy1heptanone-2 and 0.1 to 0.8 percent fordiacetone alcohol.

The reaction product is colorless and clear. No harmful tarry by-productis formed at all. Taking into account the equilibrium of thecondensation reaction of acetone, the conversion is surprisingly high.Thus, the process according to the present invention enables theconversion of acetone into MIBK directly in one-stage operation withboth high conversion and high selectivity.

The present invention is illustrated in more detail by the followingexamples which are not to be construed to restrict the scope of theinvention.

EXAMPLE 1 The catalyst used was prepared by impregnating Molecular Sieve13X (in the form of pellet having a size of one-sixteenth inch, aproduct marketed by Linde Company) with an aqueous solution (containing2 percent of l-lCl) of palladium chloride at 25 C. for 60 minutes, and,after being dried, reducing with hydrogen at 200 C. The amount ofpalladium metal supported on the pellet was 0.4 percent by weight. 30ml. of acetone and 10 ml. of the above catalysts were introduced into anautoclave having the capacity of 100 ml. and provided with a stirrer,and the autoclave was heated to a temperature of 180 C. in an oil bath.Hydrogen was then introduced to a total inside pressure of 17 kg./cm",the partial pressure of hydrogen inside the autoclave being 2 kg./cm(the vapor pressure of acetone is 15 kg./cr n at 180 C.). As thereaction proceeded fresh hydrogen was introduced intermittently tocompensate the pressure drop and restore the total pressure to itsinitial level of 17 kg./cm After 4 hours of reaction the autoclave wascooled and the reaction product, discharged from the autoclave, wasanalyzed by means of gas chromatography after removal of hydrogen. Theconversion of acetone was 43.8 percent. and the selectivities were 95.8percent for MIBK, 0.8 percent for mesitylene, 2.0 percent for isopropylalcohol, 1.2 percent for diisobutyl ketone, and 0.2

percent for diacetone alcohol. The reaction product was clear andcolorless.

EXAMPLE 2 A palladium-carbon catalyst was prepared by impregnatingactive carbon with a solution (containing 2 percent of HCl) of palladiumchloride at C. for 60 minutes, and reducing, after being dried, with analkaline aqueous solution of hydrazine at 40 C. ml. of acetone, 10 ml.of "Molecular Sieve 13X" (pellet; size: one-sixteenth inch marketed byLinde Company) and 5 ml. of the palladium-carbon catalyst wereintroduced into an autoclave of 100 ml. capacity equipped with astirrer. The autoclave was immersed in an oil bath and was heated to atemperature of 200 C. Hydrogen was then introduced into the autoclave toa total inside pressure of 28 kg./cm the partial pressure of hydrogeninside the autoclave being 5.5 kgJcm (the vapor pressure of acetone is22.5 1 g./cm at 200 Q). As the reaction proceeded fresh hydrogen wasintroduced intermittently into the autoclave to compensate the decreasedamount of hydrogen and maintain the inside pressure at 28 leg/cm. After4.5 hours of reaction, the autoclave was cooled and the reaction productdischarged from the autoclave was analyzed by means of gaschromatography after removal of hydrogen. The conversion of acetone was52.4 percent and the selectivities were 96.3 percent for MIBK, 0.9percent for mesitylene, 0.9 percent for isopropyl alcohol, 1.5 percentfor diisobutyl ketone and 0.4 percent for diacetone alcohol. Thereaction product was clear and colorless.

EXAMPLE 3 The catalyst used was prepared by reducing Palladium- Alumina[marketed by Nippon Engelhardt Company; pellet (3 mm in diameter and 3mm in hight); palladium content 0.5 percent] in the hydrogen stream at200 C. 30 m1. of acetone and 10 ml. of the catalyst were introduced intoan autoclave of ml. capacity provided with a stirrer, and the autoclavewas immersed in an oil bath and was heated to C. Hydrogen was thenintroduced into the autoclave to a total inside pressure of 16.5 kg./cmthe partial vapor pressure of hydrogen in the autoclave being 1.0 kglcm(the vapor pressure of acetone is 15.5 kgjcm at 180 Q). As the reactionproceeded fresh hydrogen was introduced intermittently to compensate thedecreased amount of hydrogen and maintain the inside pressure at 16.5kg./crn". After 3.5 hours of reaction the autoclave was cooled and thereaction product discharged was analyzed by means of gas chromatographyafter removal of hydrogen and the catalyst. The conversion of acetonewas 48.1 percent and the selectivities were 94.2 percent for MIBK. 0.6percent for isopropyl alcohol, 0.1 percent for mesityl oxide, 3.0percent for diisobutyl ketone, 1.5 percent for 4,6- dimethylheptanone-Z,0.4 percent for diacetone alcohol, and 0.2 percent for unidentifiedsubstances. The reaction product was clear and colorless.

EXAMPLE 4 The catalyst used was prepared by impregnating Active Alumina"(spherical; marketed by Norton Company) with an aqueous solutioncontaining 2 percent of HCl of palladium chloride at 25 C. for 60minutes and, after being dried, reducing with hydrogen at 300 C. Theamount of palladium supported on the alumina was 0.35 percent. 30 ml. ofacetone and 10 ml. of the above catalyst were introduced in theautoclave of 100 ml. capacity provided with a stirrer, and the autoclavewas heated to a temperature of 180 C. in an oil bath. Hydrogen was thenintroduced to a total inside pressure of 17.5 kgJcrn at 180 C., thepartial pressure of hydrogen in the autoclave being 2.0 kgJcm As thereaction proceeded fresh hydrogen was introduced intermittently tocompensate the decreased amount of hydrogen and maintain the insidepressure at 17.5 kg./cm After 3.5 hours of reaction the autoclave wascooled and the reaction product discharged was analyzed by means of gaschromatography, after removal of hydrogen and the catalyst. Theconversion of acetone was 42.3 percent and the selectivities were 95.6percent for MIBK, 0.3 percent for isopropyl alcohol, 0.1 percent formesityl oxide, 2.2 percent for diisobutyl ketone, 1.3 percent for4,6-dimetylpentanone-2, 0.4 percent for diacetone alcohol, and 0.1percent for unidentified substances. The reaction product was clear andcolorless.

EXAMPLE 5 The catalyst used was prepared by impregnating Active Alumina(spherical; marked by Norton Company) with an aqueous solutioncontaining 2 percent of HCl of the mixture of thorium nitrate andpalladium chloride at 25 C. for 60 minutes, heating the dried materialin the air at 400 C., and reducing then with hydrogen at 300 C. Theamount of thorium oxide and palladium metal supported on active aluminawas 5 percent and 0.35 percent respectively. 30 ml. of acetone and ml.of the catalyst prepared as above were introduced in an autoclave of 100ml. capacity provided with a stirrer, and the autoclave was heated to atemperature of 1 80" Ciin an oil bath. Hydrogen was then introduced to atotal inside pressure of 17.5 kg./cm at 180 C., the partial pressure ofhydrogen in the autoclave being 2.0 kgJcm As the reaction proceededfresh hydrogen was introduced intermittently to compensate the decreasedamount of hydrogen and maintain the inside pressure at 17.5 kg./cm"'.After 3.5 hours of reaction the autoclave was cooled and the reactionproduct discharged was analyzed by means of gas chromatography afterremoval of hydrogen and the catalyst. The conversion of acetone was 56.1percent and the selectivities were 93.3 percent for MIBK, 0.2 percentfor isopropyl alcohol, 0.05 percent for mesityl oxide, 4.0 percent fordiisobutyl ketone, 2.3 percent for 4,6- dimethylpentanone-Z, 0.1 percentfor diacetone alcohol and 0.05 percent for unidentified substances. Thereaction product was clear and colorless.

EXAMPLE 6 The catalyst used was prepared by impregnating Active Alumina(spherical; marketed by Norton Company) with an aqueous solution(containing 2 percent of HCl) of the mixture of zirconium nitrate andpalladium chloride at C. for 60 minutes, drying at 130 C. after removalof the excess solution, heating in the air at 400 C. for 5 hours, andreducing with hydrogen at 300 C. The amount of zirconium oxide andpalladium metal supported on active alumina was 5 percent and 0.35percent respectively. ml. of acetone and 10 ml. of the above catalystwere introduced in an autoclave of 100 ml. capacity provided with astirrer, and the autoclave was heated to a temperature of 140 C. in anoil bath. Hydrogen was then introduced into the autoclave to a totalinside pressure of 8 leg/cm at 140 C., the partial pressure of hydrogenin the autoclave being 1.0 kg./cm As the reaction proceeded freshhydrogen was introduced intermittently to compensate the decreasedamount of hydrogen and maintain the inside pressure always at 8 kg./cmAfter 3.0 hours of reaction, the autoclave was cooled and the reactionproduct discharged was analyzed by means of gas chromatography afterremoval of hydrogen and the catalyst. The analytical result showed thatthe conversion of acetone was 43 percent and the selectivities were 93.9percent for MIBK, 0.2 percent for isopropyl alcohol, 0.06 percent formesityl oxide, 3.8 percent for diisobutyl ketone, 1.7 percent for4,6-dimethylheptanone-2, 0.32 percent for diacetone alcohol and 0.02percent for unidentified substances. The reaction product was clear andcolorless.

EXAMPLE 7 The catalyst used was prepared by impregnating Active Alumina(a product of Sumitomo Chemical Company, designated as KH-lZ") with anaqueous solution (containing 2 percent of HCl) of the mixture ofzirconium nitrate and palladium chloride at 20 C. for 60 minutes, dryingat 130 C. after removal of the excess solution, heating in the air at400 C. for 5 hours, and reducing with hydrogen at 300 C. The amount ofzirconium oxide and palladium metal supported on the active alumina was5.5 percent and 0.37 percent respectively. 30 ml. of acetone and 10 ml.of the above catalyst were introduced into an autoclave of ml. capacityprovided with a stirrer, and the autoclave was heated to a temperatureof 140 C. in an oil bath. Hydrogen was then introduced into theautoclave to a total inside pressure of 8 kg./cm at 140 C., the partialpressure of hydrogen in the autoclave being 1.0 kg./cm As the reactionproceeded, hydrogen was introduced intermittently to compensate theincreased amount of hydrogen in the autoclave and maintain the totalpressure always at 8 leg/cm. After 3.2 hours of reaction, the autoclavewas cooled and the reaction product discharged was analyzed by means ofgas chromatography after removal of hydrogen and the catalyst. Theanalytical result showed that the conversion of acetone was 47 percentand the selectivities were 94.0 percent for MIBK, 0.12 percent forisopropyl alcohol, 0.07 percent for mesityl oxide, 3.7 percent fordiisobutyl ketone, 1.8 percent for 4,6-dimethylheptanone-2, 0.3 percentfor diacetone alcohol and 0.01 percent for unidentified substances. Thereaction product was clear and colorless.

EXAMPLE 8 The catalyst used was prepared by impregnating Active Alumina"(spherical; marketed by Norton Company) with an aqueous solution(containing 2 percent of HCl) of the mixture of chromium nitrate andpalladium chloride at 25 C. for 60 minutes, drying at C., heating in theair at 400 C., for 5 hours and reducing with hydrogen at 300 C. Theamount of chromium oxide and palladium metal supported on the activealumina was 5 percent and 0.35 percent respectively. 30 ml. of acetoneand 10 ml. of the above catalyst were introduced into an autoclave of100 ml. capacity provided with a stirrer, and the autoclave was heatedto a temperature of C. in an oil bath. Hydrogen was then introduced intothe autoclave to a total inside pressure of 8 kg./cm at 140 C., thepartial pressure of hydrogen in the autoclave being 1.0 kg./cm As thereaction proceeded fresh hydrogen was introduced to compensate thedecreased amount of hydrogen and maintain the total pressure always at 8kg./cm After 3.5 hours of reaction, the autoclave was cooled and thereaction product discharged was analyzed by means of gas chromatographyafter removal of hydrogen and the catalyst. The analytical result showedthat the conversion of acetone was 45 percent and the selectivities were93.7 percent for MIBK, 0.21 percent for isopropyl alcohol, 0.05 percentfor mesityl oxide, 3.9 percent for diisobutyl ketone, 1.8 percent for4,6-dimethylheptanone-2, 0.32 percent for diacetone alcohol and 0.02percent for unidentified substances. The reaction liquid was clear andcolorless.

What is claimed is:

l. A one-stage process for producing methyl isobutyl ketone from acetoneand hydrogen, which comprises contacting acetone in the liquid phasewith hydrogen in the presence of a catalyst selected from the groupconsisting of:

a. Palladium and thorium oxide on activated alumina,

b. Palladium and zirconium oxide on activated alumina, and

c. Palladium, thorium oxide and zirconium oxide on activated alumina ata temperature of from 100 to 250 C. under a total pressure of the vaporpressure of acetone corresponding to the reaction temperature and apartial pressure of hydrogen of 0.1 l0 kglcm 2. The process according toclaim 1, wherein the amount of palladium supported on the alumina is 0.1to 5 percent by weight of the alumina, wherein the amount of thoriumoxide and/or zirconium oxide is 2 to 30 percent by weight of thecatalyst, and wherein the reaction temperature is from 130 to 2 10 C.

2. The process according to claim 1, wherein the amount of palladiumsupported on the alumina is 0.1 to 5 percent by weight of the alumina,wherein the amount of thorium oxide and/or zirconium oxide is 2 to 30percent by weight of the catalyst, and wherein the reaction temperatureis from 130* to 210* C.